CN101222866B - Refrigerated display case having a transparent insulating glazing unit - Google Patents
Refrigerated display case having a transparent insulating glazing unit Download PDFInfo
- Publication number
- CN101222866B CN101222866B CN200580049882.XA CN200580049882A CN101222866B CN 101222866 B CN101222866 B CN 101222866B CN 200580049882 A CN200580049882 A CN 200580049882A CN 101222866 B CN101222866 B CN 101222866B
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- China
- Prior art keywords
- glass plate
- glass
- gas
- outside
- plate
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Classifications
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47F—SPECIAL FURNITURE, FITTINGS, OR ACCESSORIES FOR SHOPS, STOREHOUSES, BARS, RESTAURANTS OR THE LIKE; PAYING COUNTERS
- A47F3/00—Show cases or show cabinets
- A47F3/04—Show cases or show cabinets air-conditioned, refrigerated
- A47F3/0404—Cases or cabinets of the closed type
- A47F3/0426—Details
- A47F3/0434—Glass or transparent panels
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
- C03C27/06—Joining glass to glass by processes other than fusing
-
- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B3/00—Window sashes, door leaves, or like elements for closing wall or like openings; Layout of fixed or moving closures, e.g. windows in wall or like openings; Features of rigidly-mounted outer frames relating to the mounting of wing frames
- E06B3/66—Units comprising two or more parallel glass or like panes permanently secured together
- E06B3/677—Evacuating or filling the gap between the panes ; Equilibration of inside and outside pressure; Preventing condensation in the gap between the panes; Cleaning the gap between the panes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
- Y10T428/1317—Multilayer [continuous layer]
- Y10T428/1321—Polymer or resin containing [i.e., natural or synthetic]
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Thermal Sciences (AREA)
- Joining Of Glass To Other Materials (AREA)
- Surface Treatment Of Glass (AREA)
- Securing Of Glass Panes Or The Like (AREA)
- Refrigerator Housings (AREA)
- Laminated Bodies (AREA)
- Specific Sealing Or Ventilating Devices For Doors And Windows (AREA)
- Freezers Or Refrigerated Showcases (AREA)
Abstract
The invention concerns an insulating glazing wherein the gap between the substrates is filled with at least one rare gas such as argon, krypton or xenon, the inter-layer sheet (50) has a thermal conductivity less than 1 W/m.K, preferably less than 0.3 W/m.K, a low-emissive coating being deposited on at least part of one of the substrates, an anti-frost coating being deposited on part of at least the outer surface of one substrate, the glazing being free of heating element, the glazing having a thermal conductivity coefficient U less than 1.2 W/m.K with a gas filling of at least 85 %, and having a light transmission of at least 67 % and a light reflection less than 18 %.
Description
The present invention relates to the heat insulation window glass for processing refrigeration case, i.e. the container of cold or snap frozen product (for example Foods or drinks) contact, or need any other products of freezing, for example medicine or even fresh flower.This heat insulation window glass is made up of at least two kinds of glass plate base materials, and they are separated by gas blanket, and wherein at least one base material has low emission coating.
The product being kept in refrigeration case should be still visible, when being this situation in many effective sales place, is equipped with the refrigeration case of glazed plate portion, and its refrigeration case is become freezing " glass plate cabinet " by it, and its adopted name is " reach in freezer of selling goods ".These " glass plate cabinets " have multiple modification.Some " glass plate cabinets " have the shape of cabinet, and at this moment it itself is transparent, other be box shape, its horizontal case lid is made with glass plate, to can see its content.In the showcase of these types, need to allow client still can fully see these commodity, just can these commodity of preliminary election to do not open " glass plate cabinet ".
But one of them basic problem that these glass plate cabinets run into is the door leaf outside fogging in shop side.In fact, this outside is by refrigeration environment cools, and this environment is in opposing face, with the inner face side of this internal tank environmental exposure, simultaneously much higher with water content, also much higher environment atmosphere contact of temperature; There is water smoke, the visuality that hinders like this commodity during lower than dew-point temperature in the temperature of this outer surface.
Another major issue is also fogging in the time opening glass plate cabinet and get these commodity, even on door leaf inner face, forms frost.In fact, in unusual low temperature, even lower than the glass plate substrate surface of 0 DEG C, at this moment much higher with water content, also much higher ambiance contact of temperature; This interior base material temperature, at this moment lower than dew-point temperature, causes like this on this base material condensation occurs, when even this base material temperature is negative with regard to frosting.The existence of steam or frost hinders the visibility of commodity, and will spend a few minutes, and even dozens of minutes reaches steam or frost are disappeared completely.
In order to limit these defects, once imagination has the glass plate that strengthens heat-proof quality in the prior art, has bilayer or the triplex glass plate of one or more low emission coatings, and it heats with the inner base material contacting of shell.
In addition, known by patent application WO 03/008877, the enhancing heat insulation window glass of refrigeration case should ensure that according to this file the steam on the door leaf outside of shop one side disappears.
This class heat insulation window glass is made up of triplex glass plate, it comprises three thickness 3mm glass plate base materials, 8 or 13mm same thickness gas blanket that they are made up of air, argon gas or Krypton separate, and two low emission coatings are placed in this glass plate the 2nd and 5 upper (starting to calculate from the Locating Glass plate outermost being enclosed in this shell).
According to this part of file, the heat transfer coefficient U of this glass plate is less than or equal to 0.2BTU/ hour. square feet F or 1.11W/m
2.K.Associate 1.0W/K.m
2corresponding to 0.18BTU/ hour. square feet F.
In the time of door leaf closed position, improve heat transfer coefficient U and ensure that the temperature that may have with respect to the cold environment because of at its opposite face outside this is relatively hot; Therefore this outside in shop side is the temperature higher than dew point, while avoiding like this this glass plate cabinet to close, on this outside, forms steam, and therefore not needing has heating element heater on base material outside.
But, if solved the steam defect of shop side, case side frost exist defect still potential.In fact, so a kind of glass plate need to postpone certain hour, and even a few minutes, to ensure that the frost on this glass plate inner surface disappears.In addition, due to heat transfer coefficient, U is relatively good, should be colder with the outer surface of the interior substrate of this refrigeration environmental exposure, and be conducive to like this improve and in the time opening glass plate cabinet, on this substrate, form frost amount, and extend the time limit that frost disappears.
In addition, in order to solve this rear defect, avoid or make disappearing fast with the steam forming on the glass plate inner face contacting in housing or frost, considering to place heating element heater on this glass plate inner face with known way as already mentioned.
But, the electric energy that some refrigeration glass plate cabinets consume like this, the electric energy consuming due to the heating element heater being placed on these substrates especially, in the meaning of energy economy, pure is not troubling from environment and sustainable development aspect current events, and for these shops, is expensive yet.
In addition, the difference in functionality layer of use, comprising low emission coating, makes the light transmission variation of glass plate in a known way.In order to ensure correctly to see these commodity from housing outside, the people assembling shell inside that do not hesitate, illumination, it also must cause heat release except consuming additional energy, therefore may make front be subject to degenerate according to the freezing quality of product, and cause the extra consumed energy of corresponding refrigeration unit.
Therefore, the object of this invention is to provide a kind of optimization solution that strengthens hot property heat insulation window glass that has, it is attempted for refrigeration glass plate cabinet, avoid all formation steam or frost, even in internal and external environment and the solution of opening under the hard situation of glass plate cabinet frequency and time, this time is corresponding to using this glass plate cabinet or resupplying the needed time of commodity for this glass plate cabinet, and be function admirable according to energy economy, and ensure to be placed on the product quality in described glass plate cabinet, comfortable as seen.
In description, " inside " and " outside " should be appreciated that and be below, when this door leaf is in the closed position, or outside element modifier inner towards refrigeration case respectively.
" inner " and " outside " should be appreciated that it is respectively towards the inside and outside element modifier of heat insulation window glass.
According to the present invention, the heat insulation window glass that is used in particular for refrigeration chamber door door leaf comprises at least two glass substrates, at least one deck low heat conductivity interlayer, it makes these two substrates keep spaced apart, the low emission coating of one deck, it is deposited on wherein at least one substrate at least in part, it is characterized in that:
The thermal conductivity of-this interlayer, lower than 1W/m.K, is preferably lower than 0.3W/m.K,
-at least one rare gas of space-filling between at least two substrates,
-this glass plate does not have heating element heater,
The thermal conductivity factor U of-this glass plate is less than 1.2W/m
2.K, be preferably less than 1.15W/m
2.K, wherein blanketing gas at least 85%,
The light transmission of-this glass plate is at least 67%, and light reflects lower than 18%,
-this glass plate is also included in the anti-fog coatings on substrate at least a portion outside.
According to a feature, this gas is selected from argon gas, Krypton and xenon.
According to another feature, low emission coating is at least on glass-board surface 2 and/or 3 and/or 4.
These glass-board surface numberings 1-4 is that double glazing unit or 1-6 are triplex glass plate, these faces of this glass plate, and for example face 1, corresponding to the glass plate outside contacting with ambiance, and face 4 or 6 is respectively corresponding to the surface contacting with refrigeration case.
Preferably, anti-reflectance coating is deposited on wherein at least one substrate, preferably on the face 1 and/or face 3 and/or face 5 of glass plate.
According to first embodiment of the present invention, this heat insulation window glass is triplex glass plate, it comprises three glass substrates, first substrate, its outside is used for contacting with enclosure interior in the time that door leaf is in the close position, second substrate or Intermediate substrate, and the 3rd substrate, its outside is used for and hull outside environmental exposure, and they separate with low heat conductivity interlayer to each other
-these substrate thickness are 2-5mm, preferably equal 3 or 4mm,
At least one rare gas of at least one space-filling between-these substrates,
The thickness of-gas blanket is 4mm at least,
-low emission coating is deposited on the face 2 and/or 4 of glass plate,
It is upper that-anti-fog coatings is deposited on the 3rd substrate at least a portion outside,
The thermal conductivity factor U of-this glass plate is less than 1.1W/m
2.K, be even less than 0.95 or 0.80, wherein blanketing gas at least 85%;
The light transmission of-this glass plate is at least 67%, and outside light reflects lower than 18%.
According to a feature, this triplex glass plate is included in the low emission coating of one deck on face 2 and 4, and its heat transfer coefficient U is less than 1.0W/m
2.K.
Advantageously, this low emission coating is deposited on the glass-board surface relevant to the thickest gas blanket.
Preferably, at least the anti-reflectance coating of one deck is deposited on one of them face of this glass plate, is preferably deposited at least one face of face 1,3 or 5.
According to a specific embodiments, the thickness of one of them gas blanket is 8mm, and the thickness of another gas blanket is 10mm at least, and these gas blankets are argon gas.
According to another specific embodiments, one of them gas blanket is Krypton, and its thickness is 8mm, and another gas blanket is air, and its thickness is 10mm at least.
According to second embodiment of the present invention, this heat insulation window glass is double glazing unit, it comprises two glass substrates, first substrate, its outside is used for contacting with enclosure interior in the time that door leaf is in the close position, second substrate, its outside is used for and hull outside environmental exposure, they separate with low heat conductivity interlayer to each other, a kind of rare gas of space-filling between these substrates
-these substrate thickness equal 3 or 4mm,
At least one rare gas of space-filling between-these substrates,
-gas layer thickness is 8mm at least,
-low emission coating deposition at least on glass-board surface 2,
It is upper that-anti-fog coatings is deposited at least a portion first substrate outside,
The thermal conductivity factor U of-this glass plate is less than 1.15W/m
2.K, blanketing gas at least 85% wherein;
Light transmission at least 75% and the outside light of-this glass plate reflect lower than 12%.
According to a feature, according to this second embodiment, another low emission coating is deposited on this glass-board surface 3.
Preferably, its thermal conductivity factor U is less than 1.05W/m
2.K, wherein blanketing gas is at least 92%.
According to a specific embodiments, this gas blanket is Krypton.
According to another specific embodiments, this gas blanket is xenon, and its thickness is 8mm.
Advantageously, this double glazing unit is included in the anti-reflectance coating of face 1 and/or 3, and its light transmission is more than 80%, and outside light reflects lower than 10%.
Another feature of heat insulation window glass according to the present invention, this anti-fog coatings is such, glass plate without anti-fog coatings is reduced at the most-30 DEG C in its coated side and temperature, when the environmental exposure of especially-15 DEG C ,-18 DEG C or-24 DEG C, then at least equal 0 DEG C with temperature, preferably 10-35 DEG C, 15-30 DEG C especially, especially when the contact of the atmosphere of 23-27 DEG C and at least 25% residual humidity, at 12s at least, preferably 1min at least, 2min at least especially, does not form any frost in even at least growing to during 3min.
This anti-fog coatings contains falls low-freeing anti-gel compound, for example salt, KCl, NaCl or equivalent solution and/or alcohol and/or the optionally suitable hydrophilic polymer in water especially, copolymer, prepolymer or oligomer, and anti-fog coatings optionally contains one or more surfactants, this compound optionally has hydrophobic property on one part surface.
Advantageously, this anti-gel compound and at least one other compound use, to reach physics or chemical interaction, ensure that machinery strengthens coating.
This anti-gel is for example PVP, and it and polyurethane use, to produce Physical interaction, maybe may relate to polyalcohol, it and at least one isocyanate-functional generation chemical interaction that associates.
According to another feature of heat insulation window glass, interlayer between these substrates comprises the first hermetic barrier layers according to an embodiment, it is made up of the body made from styrene-acrylonitrile (SAN) or PP type thermoplastic, this thermoplastic mixes with glass plate and sheet metal class, aluminium or stainless steel-like fortifying fibre, therefore partly cover this thermoplastic, and multiple sulfides the second hermetic barrier layers to these liquid and this steam.
According to another embodiment of interlayer, it is to be made up of the substantially flat section bar at least a portion glass plate periphery, this section bar is connected with these substrate portion, and by stainless steel, aluminium or there is reinforced fiber plastics and form, and be included in the metal coating on the face contrary with this gas blanket, it forms the hermetic barrier layers to steam, gas and liquid.In addition, this interlayer bending-resistant linear intensity is 400N/m at least.
Preferably, these outside substrates of heat insulation window glass at least of the present invention are made with toughened glass plate.
Above-mentioned like this sign heat insulation window glass is advantageously used for a door leaf, especially the door leaf of refrigeration case.
This door leaf comprise for support glass plate when thering is the framework that heat bridge fracture property aluminium forms, it is at the overall heat-transfer coefficient U of blanketing gas at least 92%
wadvantageously be less than 1.25W/m
2.K.
This door leaf comprises the framework being made up of PVC, and it is at the overall heat-transfer coefficient U of blanketing gas at least 92%
wbe less than 1.20W/m
2.K.
So the inventor proves this glass plate different characteristic composite type, this glass plate when the refrigeration chamber door door leaf, should prove to ensure that this glass plate is heat insulation, this glass plate light transmission and respectively in this glass plate outside and the inner best solution that does not form steam and frost.
So the present invention relates to the combination of the whole features of this glass plate, they are the anti-fog layer of thickness, gas type, sandwich type, use functional coating type and position thereof, this glass plate heat transfer and the existence of this gas blanket in particular.
To realize other advantage of the present invention and feature by being not drawn to scale brief description of the drawings below, wherein Fig. 1 and 2 illustrates respectively two fragmentary cross-sectional views of two glass plate embodiments of the present invention.Fig. 1 is according to three layers of heat insulation window glass 10 of first embodiment explanation according to the present invention, its blanketing gas, without heating element heater and comprise at least one low emission coating 30 and anti--white coating 40, and its heat transfer coefficient U is less than 1.2W/m
2.K, be preferably less than 1.15W/m
2.K, wherein blanketing gas rate is at least 85%, and outside light transmission at least 67% and light reflect lower than 18%.
Triplex glass plate 10 comprises three glass substrates, first substrate or interior substrate 11, its outside 11a is used for contacting with this enclosure interior in the time that door leaf is in the close position, second substrate or Intermediate substrate 12, and the 3rd substrate or outside substrate 13, its outside 13a for and hull outside environmental exposure.First and the 3rd substrate 11 and 13 preferably make with toughened glass plate.
These real estates are designated as 1-6, and in upper filling source, figure (1)-(6), and respectively corresponding to outside 13a, it for hull outside environmental exposure, until face 11a, it for contacting with enclosure interior in the time that door leaf is in the close position.
The thickness of every substrate is 2-5mm, it preferably 3 or 4mm so that make this glass plate gross weight minimum with optimize this smooth transmission.
Each other by low heat conductivity interlayer 50 separately, this interlayer can be made up of two horse shape different elements or single horse shaped element part on this Intermediate substrate these substrates.The thermal conductivity factor of this interlayer is 1W/m.K (being 1.88BTU/hr.ft.F) at the most, is preferably less than 0.7W/m.K, is even less than 0.4W/m.K.Should mention 0.534W/m.K corresponding to 1BTU/hr.ft.F.
Interlayer example is to be constructed as follows basic body: styrene-acrylonitrile (SAN) or PP type thermoplastic and the glass plate class fortifying fibre mixing with this thermoplastic, and gas and water vapour are formed to the sheet metal of sealing, this sheet metal sticks on a part of basic body, with the part of this contrary placement in inside of glass plate space.This basis body (wherein also comprising dehydrating agent) is deposited in the periphery and separated space between these substrates.The supplementary hermetic barrier layers of these liquid and steam ensures this interlayer sealing, is made up of for example polysulfide, polyurethane or silicone, and sealing barrier layer is placed on the sheet metal side of interlayer.
When the sheet metal of this basis body be with aluminum time, a kind of like this SAN and glass plate fiber base interlayer be for example SAINT-GOBAIN GLASS company with trade name
known, this basis body sheet metal be make with stainless steel time, be with trade name SWISSPACER
known, and the interlayer of being combined with the double barrier made from polysulfide has thermal conductivity factor
for 0.64W/m.K. (being 1.20BTU/hr.ft.F), SWISSPACER
for 0.25W/m.K (or 0.47BTU/hr.ft.F).
As sandwich type, can also be set forth in the interlayer of describing in application WO 01/79644, it is by not being at this inside of glass plate but forming at its outside substantially flat section bar being connected with some substrate portion of placing.This section bar can be stainless steel or aluminium or the plastic base with fortifying fibre, and its bending-resistant linear intensity is 400N/m at least.This class interlayer comprises gas, dust and the hydraulic seal barrier layer on a face at least therein, and it is made up of metal coating or any other applicable material.
This interlayer is for example that thickness 0.5mm aluminium forms completely, its thermal conductivity factor 0.25W/m.K (being 0.47BTU/hr.ft.F).
Space between internal base plate 11 and Intermediate substrate 12 is made up of interior gas blanket 14, external substrate 13 is that outer gas blanket 15 forms with the space of Intermediate substrate 12, these gas layer thickness are 4mm at least, and adjust heat transfer coefficient U with the performance of expecting, but should not be greater than 16mm.One of them gas blanket is made up of rare gas, and this gas is selected from argon gas, Krypton or xenon according to filling rate at least 85%.In order also to improve coefficient U, preferably use at least 92% Krypton or xenon to fill.
Have multiple gas blanket in this glass plate time, one of them gas blanket can be air, and in this case, this air layer thickness is 10mm at least.
This glass plate comprises low emission coating 30, this painting is placed on the external substrate 13 at least a portion face 13b (face 2) facing to this inside of glass plate, and/or another low emission coating 31 of same type, this painting is deposited upon facing on the 11 Intermediate substrate 12 at least a portion face 12a (face 4) of substrate inside.
These low emission coatings it is also conceivable that on face 2 and 3.While just considering single coating, it is preferably placed on the face coordinating with the thickest gas layer thickness.
These low emission coatings are metal and metal oxide layer base, they can adopt distinct methods to obtain: adopt vacuum method (thermal evaporation, the cathodic sputtering strengthening with magnetron), or employing is sprayed organo-metallic compound pyrolysis by carrier gas with liquid, solid or gas form on this heated substrates surface.
Preferably, these metal levels are money bases, and these metal oxide layers are zinc, tin, titanium, aluminium, nickel, chromium, antimony (Sb) compound, the mixture-base of at least two kinds of compounds in nitride or these compounds, on optionally barrier layer, silver-colored upper strata, for example Ti class blocking-up metal or blocking-up metal alloy.
As an example, can enumerate following lamination, wherein symbol (TiO
2) represent to relate to a kind of optional elements:
Glass/SnO
2/ (TiO
2)/ZnO/Ag/Ti or NiCr or NiCrO
x/ ZnO/SnO
2or Si
3n
4/ SnZnO
x: Sb or TiO
x
Glass/SnO
2/ TiO2/ZnO/Ag/NiCrO
x/ (TiO2)/SnO2/SnZnO
x: Sb
Especially about thickness in these lamination embodiments and compound amount more details can be referring to patent application FR2783918 or EP1042247.
According to the present invention, this types of coatings allows in this substrate optical quality, relates to especially in its visible region light transmission optics quality and its suitably compromise between infrared light district reflective qualities.In glass plate of the present invention, use the emissivity of low emission coating less than or equal to 0.3, be preferably lower than or equal 0.05, light transmission is higher than 75%, preferably higher than 85%.
In addition, should use SAINT-GOBAIN GLASS company
fUTUR N product is as the substrate with a kind of like this coating, and this product is made with thickness 4mm glass plate, and its emissivity is 0.04, and light transmission is 88.4%.
The another kind of product that the present invention is also applicable to is SAINT-GOBAIN GLASS company
uLTRA, this product is made with thickness 4mm glass plate, and its emissivity is 0.02, and light transmission is 86.7%.When so a kind of product is used for this or all these substrates, its coefficient U is according to heat insulation ratio
fUTUR N product is good, but the transmission loss of this glass plate light is slight.
In addition, on one or more substrates, preferably on face 1 and/or 3 and/or 5, can have at least anti-reflectance coating 32 of one deck, its advantage is also improved the light transmission of this glass plate except anti-reflection function, and ensures that some products have better observability in this glass plate cabinet.
Finally, this glass plate comprises anti--white coating 40, and this layer joins with the outside 11a of interior substrate 11.This coating can Direct precipitation on this substrate or be deposited on the plastic sheeting being connected with this substrate.
Especially, when this glass plate has this anti-fog coatings, this coating is reduced to many-30 DEG C in this coated side and temperature, especially-15 DEG C, the environmental exposure of-18 DEG C or-24 DEG C, then at least equals 0 with temperature, preferably 10-35 DEG C, 15-30 DEG C especially, the more particularly atmosphere of 23-27 DEG C contact, and contact with at least 25% residual humidity, at 12s at least, preferably 1min at least, 2min at least especially, even grows at least 3min and does not form any frost.According to standard EN 441, be given in 3 minutes values under common employing condition in shop, as can be seen here, this coating also realizes its anti-frosting function in the time of any opening, as long as it is any time lower than 3min that door leaf is opened frequency, the temperature of this coated side is equal to or less than 0 DEG C and rises, and the temperature of opposition side is positive temperature, is even attended by very large humidity.
This anti-fog coatings be have absorption property with absorbefacient.
Arriving substrate surface from hydrone, to be hung in its table surface, and with its surperficial connection, make like this coating play fully in this meaning of absorption function effect and say, it has absorption property.
This coating is absorbefacient (hydrophilic), so it is absorbed because of these hydrone infiltrations.
This coating contains falls low-freeing anti-gel compound, for example salt, KCl especially, NaCl or equivalent solution and/or alcohol and/or optionally suitable hydrophilic polymer, copolymer, prepolymer or the oligomer in water, and this coating optionally contains one or more surfactants, this compound optionally has hydrophobic property on one part surface.
Therefore, this anti-gel compound can generate some keys between described compound and hydrone, stops that these hydrones are connected to each other to form to form white crystalline.
Use especially ethanol, isopropyl alcohol as the alcohol in this anti-gel compound.Form these hydrophilic polymers of this solution, copolymer, prepolymer or oligomer gather the PVP of (n-vinyl-2 pyrrolidones) or poly-(1-vinyl pyrrolidone) class in particular, poly-(n-vinyl-2 pyridine) class, poly-(n-vinyl-3-pyridine) class, the polyvinylpyridine of poly-(n-vinyl-4-pyridine) class, the polyacrylate of poly-(2-hydroxyethylmethacry,ate) class, poly-(N ', N-hydroxyacrylamide), polyvinyl acetate, polypropylene nitrile, for example polyvinyl alcohol, polyethylene glycol, polypropylene glycol, the polyacrylamide of the polyalcohols of PEO.Especially, these copolymers are monomers of forming these polymer taking at least one as base.
Select hydrophilic polymer and porosity can regulate especially the speed and the capacity that absorb water.This layer of advantageously 0.1-100cm of porosity
3/ g, is preferably lower than 20cm
3/ g.Porosity is defined as the vacuum hole volume of every layer of mass unit.
Can enumerate as surfactant the compound that some contain hydrophilic segment Y, it can be straight chain, side chain or unsaturated aliphatic chain or aromatics or alkyl aromatic chain, and ion or nonionic water-wet side.
Its some examples are:
-anion surfactant: Y-CO
2" M
+; Y-OSO
3" M
+; Y-SO
3" M
+; Dodecyl benzene sulfonate; Alkylsulfonate; Aliphatic acid and sulfonated fatty acid ester; Alkyl aryl sulfonate;
-cationic surfactant: Y-(R)
nnH
+ (4-n), X "; Y-R
4n
+, X "; Alkyl trimethyl ammonium; Alkyl benzyl dimethyl ammonium; Diimidazole salt; Amine salt;
-amphion: Y-N
+... CO
2"; Y-N
+... SO
3"; Betaine; Sulfenyl betaine; Imidazole salts;
-nonionic: Y-OR; Y-OH; Y-CO
2r; Y-CONHR; Y-(CH
2 -cH
2-O)
n-; Polyalcohol; Alcohol; Acid; Ester; Polyethoxylated fatty alcohol.
In addition, study the durability of this coating anti-frosting function, may need like this to improve the mechanical strength of the layer of integrating this anti-gel compound, it can bear accidental Mechanical Contact especially, or bears cleaning etc.After this finishes, this anti-gel compound may be cross-linked and/or be combined with at least one other compound, to make itself and Physical interaction or chemical interaction stable, and/or be for example dispersed in organic or inorganic solid matrix, or in ORMOCER class mixed-matrix (Organically Modified Ceramics) or colloidal sol colloidal sol.
Physical interaction should be appreciated that it is hydrogen bond, Van der Wals class polar interaction or the hydrophobic interaction that can realize the mechanical humidification similar to crosslinked action.For example using as the PVP of anti-gel compound with mix and realize this Physical interaction as the polyurethane of the substrate compound of described anti-gel compound.
This chemical interaction is that anti-gel compound and at least one other compound produce covalent bond each other, and such produced this interaction, allows this mixture carry out for example heat treatment in a known way, and UV is crosslinked, normal temperature crosslinked etc.Therefore possible that allow and mix with other compound that contains isocyanate-functional as the polyalcohol of anti-gel compound, heat this mixture and obtain a kind of polyurethane, it has the hydrophilic functional of each anti-gel compound, and chemically interactive mechanical strength between these hydroxyl-functionals and these isocyanate-functionals of polyalcohol.
For the special example of composition, can be referring to patent application WO 00/71481 and FR 0550271.In this first embodiment of the present invention, according to the expected performance of heat transfer coefficient U and follow a kind of half-way house to this glass plate, its weight and optical quality accumulation, can expect multiple specific embodiments.
Following table 1 has been collected multiple embodiment A-E of triplex glass plate, and they meet the heat-proof quality that people expect, do not form steam and frost, without heating glass plate.
In this table, list this glass plate gross thickness, these thickness of glass substrate, comprise glass plate this or these face, these gas layer thickness, gas type, the use light transmission that some glass plates ensure like this of low emission coating and the reflection of outside light, with respect to the heat transfer coefficient U that selects gas and blanketing gas rate (85% or 92%) glass plate that this embodiment obtains, and add the door leaf overall heat-transfer coefficient U of more such glass plates
w.
For each embodiment:
In-two glass plate spaces, the low heat conductivity interlayer 50 in each space is made up of two different elements; It is corresponding to the product of above-mentioned SAINT-GOBAIN GLASS company
-low emission coating 30 and 31 is deposited on some glass substrates, and they are corresponding to the product of SAINT-GOBAIN GLASS
fUTUR N, except embodiment A 1, it is corresponding to embodiment A, and wherein one of these substrates are by SAINT-GOBAIN GLASS's
uLTRA replaces, and its characteristic is described above;
On this glass substrate of-anti-fog coatings 40 Direct precipitations; Relate to the coating that SAINT-GOBAIN GLASS company sells
On-anti-reflectance coating 32 some glass substrates of deposition, and corresponding to the product of SAINT-GOBAIN GLASS
The glass plate heat transfer coefficient U having calculated at glass plate center according to standard prEN 673et prEN 410; In addition, this calculating and sandwich type are irrelevant.
Calculate and be added to respectively heat bridge fracture aluminium sash, i.e. the door leaf overall heat-transfer coefficient U of these glass plates in the common framework of some refrigeration housings and in PVC framework processed
w.According to standard EN ISO 10077-2, the size of this glass plate door leaf, framework and interlayer class and frame clsss has been considered in this calculating.
Specification 1800mm × the 800mm of this door leaf; It is 2.6W/m that the square section 40mm × 40mm of this framework and heat transfer coefficient U equal aluminium
2.K, PVC is 1.8W/m
2.K.This glass plate is the thin plate of thickness 25mm.
Table I
When one of them gas blanket (embodiment D and E) used thickness 16mm argon gas, its gas filling rate at least 85%, therefore the heat transfer coefficient U of these glass panes is less than 1.1W/m
2.K, be even less than 0.80W/m
2.K, preferably two gas blankets use Krypton and during according to filling rate at least 92% (Embodiment B) lower than 0.65W/m
2.K.
Use gas filling rate at least 92%, wherein add the door leaf overall heat-transfer coefficient U of some glass panes like this
wso be less than or equal to 1.25W/m
2.K.
So these glass panes can reach light transmission at least 67%, outside light reflects lower than 18%.The numeral that these provide considers there is anti--frost layer, and its light transmission just reduces approximately 0.5%.
Compared with embodiment A, as already explained, embodiment A 1 is used low transmitting glass substrate PLANITH
uLTRA can also improve heat-proof quality, although this glass pane also loses optical quality a little, keeps acceptable especially value.
Use anti-reflecting layer, for example anti-reflecting layer on face 1,3 and 5 (embodiment E), showing total transmittance is 79.8%, light reflection is reduced to 7.2%, therefore for this glass pane provides optical quality as snug as a bug in a rug.
Because Krypton is noble gas, from this glass plate cost consideration, just use the Embodiment C of single Krypton layer may be better than Embodiment B.
On the other hand, this Embodiment C can also prove this situation, wherein causes the gas of Embodiment B one deck in two-layer to leak completely.
Finally, estimate that in this time course in glass pane, gas loss adopts standard prEN 1279-3 to estimate to reach 1%.In addition, after for many years, glass pane gas rate is fallen, and therefore its heat-proof quality is also fallen.Starting to fill 92% gas after 7 years, showing that line and the filling rate 85% of the table of coefficient U can also be simulated the hot property of this glass pane.
Fig. 2 illustrates second embodiment of the present invention, and wherein door leaf 1 comprises double thermal insulation glass pane 20, and it fills xenon and/or Krypton and/or argon gas, there is no heating element heater, also comprises at least low emission coating 30 of one deck and anti--white coating 40.The heat transfer coefficient U of this double pane glass is less than 1.2W/m
2.K, be preferably less than 1.15W/m
2.K., light transmission at least 75%.
This double pane glass 20 comprises two glass substrates 21 and 22, and they are respectively used to contact with external environment condition with refrigeration case environment.They are separated by a low heat conductivity interlayer 50, the low heat conductivity interlayer of for example describing in first embodiment.
Between two substrates, the thickness of gas blanket 23 is 4-16mm, preferably 8mm at least.
Low emission coating 30 is placed at least one inner surface of this glass pane, on face 2 and/or face 3.This coating is in first embodiment, to describe the type of coating, silver-colored and metal oxide based.
Anti--white coating 40 is deposited on the outside 21 of internal base plate, and corresponding to the prevent-white coating of describing in first embodiment.
On at least one substrate, preferably on the face 1 and/or 3 of this glass plate, can there is anti-reflectance coating 32.
Lower Table II has illustrated the present invention three double pane glass embodiment F, G and H.Calculate the heat transfer coefficient U at glass pane center according to standard prEN 673 and prEN410; In addition, this calculating and sandwich type are irrelevant.
This low emission coating meets SAINT-GOBAIN GLASS's
fUTURN.
This anti-fog coatings meets SAINT-GOBAIN GLASS's
and this anti-reflectance coating meets the Vision-Lite of SAINT-GOBAIN GLASS
With first embodiment similarly, as previously explained, use same size, sandwich type, framework type, calculated the door leaf overall heat-transfer coefficient U that adds these class double pane glasses
w.
Table II
| Embodiment | F | G | H |
| Gross thickness (mm) | 16 | 16 | 18 |
| External substrate thickness (mm) | 4 | 4 | 4 |
| Internal base plate thickness (mm) | 4 | 4 | 4 |
| Gas pay thickness (mm) | 8 | 8 | 10 |
| Surface layer 1 | - | Antireflection | - |
| Surface layer 2 | Low transmitting | Low transmitting | Low transmitting |
| Surface layer 3 | Low transmitting | Low transmitting | Low transmitting |
| Surface layer 4 | Frost prevention | Frost prevention | Frost prevention |
| Gas pay thickness (mm) | 8 | 8 | 10 |
| Outer gas type | Xenon | Xenon | Krypton |
| Light transmission (%) | 78 | 81 | 78 |
| External reflection (%) | 9.6 | 6.0 | 9.6 |
| Coefficient U (the W/m of 85% gas rate 2.K) | 1.12 | 1.12 | 1.08 |
| Coefficient U (the W/m of 92% gas rate 2.K) | 0.99 | 0.99 | 1.01 |
| The coefficient U of 92% gas rate wAnd aluminium chassis (W/m 2.K) | 1.22 | 1.22 | 1.23 |
| The coefficient U of 92% gas rate wWith PVC framework (W/m 2.K) | 1.16 | 1.16 | 1.18 |
These are suitable for door leaf glass pane and want cube little because having the gross thickness of reduction, and therefore according to gas filling rate 85%, their heat transfer coefficient U is less than 1.15W/m
2.K, and according to gas filling rate at least 92%, lower than 1.05W/m
2.K.Therefore, the overall heat-transfer coefficient U of these door leaves
wbe less than:
According to gas filling rate at least 92% and use aluminium chassis, 1.25W/m
2.K, and according to gas filling rate at least 92% with use PVC framework, even lower than 1.20W/m
2.K.
The light transmission of embodiment F and G is at least 78%, and very advantageously by 81.5%, while adding anti-reflectance coating, light reflection is respectively 9.6% and 6.2%.
The glass pane of the present invention first and second embodiment can meet according to standard EN 441 determines environment classification 2,3,4 and 5, is listed in the table below in III, and heat transfer coefficient U is less than 0.8 especially, for example, when Embodiment B, D and E, meets classification 6.
Table III
Claims (42)
1. the double-deck or three layers of insulated glazing unit for refrigeration chamber door door leaf, it comprises at least two glass film plates, at least one layer interlayer (50), it makes these two base plates keep spaced apart, the low emission coating of one deck, it is deposited on wherein at least one base plate at least in part, it is characterized in that:
The thermal conductivity of-this interlayer is lower than 1W/m.K,
-at least one rare gas of space-filling between at least two base plates to be to form gas blanket,
-this glass plate does not have heating element heater,
-this glass plate comprises four or six,
The heat transfer coefficient U of-described glass plate is less than 1.2W/m
2.K, wherein blanketing gas at least 85%,
The light transmission of-described glass plate is at least 67%, and light reflects lower than 18%,
-described glass plate is also included in the anti-fog coatings on base plate at least a portion outside,
This low emission coating has the emissivity that is no more than 0.3 and the light transmission that is greater than 75%.
2. glass plate according to claim 1, is characterized in that, described interlayer has a thermal conductivity that is less than 0.3W/m.K.
3. glass plate according to claim 1, is characterized in that, described glass plate has the 1.15W/m of being less than
2.K heat transfer coefficient, this glass plate at least has 85% inflation filling.
4. glass plate according to claim 1, is characterized in that, described low emission coating has the emissivity that is no more than 0.05 and the light transmission that is greater than 85%.
5. glass plate according to claim 1, is characterized in that, the rare gas in the space between at least two glass film plates is selected from argon gas, Krypton and xenon.
6. glass plate according to claim 1, is characterized in that, low emission coating is at least placed on second and/or the 3rd and/or fourth face.
7. according to the glass plate described in any one claim in claim 1-3, it is characterized in that, described glass plate comprises ARC, at least one base plate.
8. glass plate according to claim 7, is characterized in that, ARC is arranged on first surface and/or the 3rd and/or the 5th.
9. three layers of insulated glazing unit according to claim 1 (10), it is characterized in that, it comprises three glass film plates, the first base plate (11), its outside (11a) for contacting with enclosure interior in the time that door leaf is in the close position, the second base plate or central floor panel (12), with the 3rd base plate (13), its outside (13a) for hull outside environmental exposure, and they are each other by interlayer (50) separately
-described base plate thickness is 2-5mm,
At least one rare gas of at least one space-filling between-described base plate (11,12,13),
The thickness of-gas blanket is 4mm at least,
-low emission coating (30,31) is deposited on second of glass plate and/or fourth face,
It is upper that-anti-fog coatings (40) is deposited on the 3rd base plate at least a portion outside (11a),
The heat transfer coefficient U of-described glass plate is less than 1.1W/m
2.K, blanketing gas at least 85% wherein;
The light transmission of-described glass plate is at least 67%, and outside light reflects lower than 18%.
10. triplex glass plate according to claim 9, is characterized in that, the thickness of described base plate equals 3 or 4mm.
11. triplex glass plates according to claim 9, is characterized in that, described glass plate has one and is less than 0.95W/m
2.K heat transfer coefficient U.
12. triplex glass plates according to claim 9, is characterized in that, described glass plate has one and is less than 0.8W/m
2.K heat transfer coefficient U.
13. triplex glass plates according to claim 9, is characterized in that, it is included in the low emission coating (30,31) on second and fourth face, and the heat transfer coefficient U of glass plate is less than 1.0W/m
2.K.
14. triplex glass plates according to claim 9, is characterized in that, this low emission coating is deposited on the glass-board surface being connected with the thickest gas blanket.
15. triplex glass plates according to claim 9, is characterized in that, at least one anti-reflectance coating is deposited on one of them face of this glass plate.
16. triplex glass plates according to claim 15, is characterized in that, at least one anti-reflective coating is deposited upon on one of them face of the first surface, the 3rd of this glass plate and the 5th.
17. triplex glass plates according to claim 9, is characterized in that, the thickness 8mm of one of them gas blanket, and at least 10mm of the thickness of another gas blanket, and these gas blankets are argon gas.
18. triplex glass plates according to claim 9, is characterized in that, one of them gas blanket is Krypton, its thickness 8mm, and another gas blanket is air, at least 10mm of its thickness.
19. double thermal insulation glass plates according to claim 1 (20), it is characterized in that, it comprises two glass film plates, the first base plate (21), its outside (21a) for contacting with enclosure interior in the time that door leaf is in the close position, the second base plate (22), its outside is used for and hull outside environmental exposure, they use interlayer (50) separately to each other, a kind of rare gas of space-filling between these base plates
-these base plate thickness equal 3 or 4mm,
At least one rare gas is filled in space (21,22) between-these base plates,
-gas blanket (23) thickness is 8mm at least,
-low emission coating deposition at least on second of glass plate,
-anti-fog coatings (40) is deposited at least a portion the first base plate (21) outside (21a),
The heat transfer coefficient U of-this glass plate is less than 1.15W/m
2.K, blanketing gas at least 85% wherein;
Light transmission at least 75% and the outside light of-this glass plate reflect lower than 12%.
20. double glazing units according to claim 19, is characterized in that, it is upper that another low emission coating (31) is deposited on the 3rd of this glass plate, and described another low emission coating has the emissivity that is no more than 0.05 and the light transmission that is greater than 85%.
21. double glazing units according to claim 20, is characterized in that, its heat transfer coefficient U is less than 1.05W/m
2.K, blanketing gas at least 92%.
22. double glazing units according to claim 19, is characterized in that, this gas blanket is Krypton.
23. double glazing units according to claim 19, is characterized in that, this gas blanket is xenon, thickness 8mm.
24. double glazing units according to claim 19, is characterized in that, it is included in the anti-reflectance coating (32) on first surface and/or the 3rd, and the light transmission of glass plate is higher than 80%, and outside light reflects lower than 10%.
25. according to the glass plate described in the claims 19, it is characterized in that, this glass plate has anti-fog coatings, when anti-fog coatings and the environment temperature of glass plate are reduced to the environmental exposure of at the most-30 DEG C, then at least equal the environmental exposure of 0 DEG C with temperature, contact at least 12s with at least 25% residual humidity, do not form any frost.
26. according to the glass plate described in the claims 19, it is characterized in that, anti-fog coatings (40) contains falls low-freeing anti-gel compound.
27. according to the glass plate described in the claims 26, it is characterized in that, anti-fog coatings (40) contains one or more surfactants.
28. according to the glass plate described in the claims 26, it is characterized in that, anti-gel compound has the hydrophobic property on one part surface.
29. glass plates according to claim 26, is characterized in that, this anti-gel compound is KCl or NaCl salting liquid.
30. glass plates according to claim 26, is characterized in that, this anti-gel compound is alcohol.
31. glass plates according to claim 26, is characterized in that, this anti-gel compound is suitable hydrophilic polymer, hydrophile copolymers, hydrophilic prepolymer or hydrophilic oligomers.
32. glass plates according to claim 26, is characterized in that, this anti-gel compound is PVP, and it and polyurethane are also with the Physical interaction that produces the described anti-fog coatings of machinery enhancing.
33. glass plates according to claim 26, is characterized in that this anti-gel compound is polyalcohol, and it is combined with at least one isocyanate-functional and produces the mechanical chemical interaction that strengthens described anti-fog coatings.
34. glass plates according to claim 1, it is characterized in that, the interlayer being placed between these base plates comprises the first hermetic barrier layers, it is made up of the body made from styrene-acrylonitrile (SAN) or polypropylene thermoplastics and sheet metal, this thermoplastic mixes with glass plate class fortifying fibre, described sheet metal partly covers this thermoplastic, described interlayer also comprises the second hermetic barrier layers of being made up of polysulfide, and it seals and make its waterproof and steam seal this glass plate.
35. glass plates according to claim 1, is characterized in that, described sheet metal is made up of aluminium or stainless steel.
36. glass plates according to claim 1, it is characterized in that, this interlayer is to be made up of substantially flat section bar at least a portion glass plate periphery, this section bar is connected with these bottom parts, and by stainless steel, aluminium or there is reinforced fiber plastics and form, and be included in the metal coating on the face contrary with this gas blanket, it forms the hermetic barrier layers to steam, gas and liquid.
37. glass plates according to claim 32, is characterized in that, this interlayer linear intensity in the time bending is 400N/m at least.
38. according to the glass plate described in the claims 1, it is characterized in that, at least outer floor (11,13,21,22) is made with toughened glass plate.
39. 1 kinds of door leaves, it adds according to glass plate described in the claims 1.
40. according to the door leaf described in claim 39, and it comprises the framework that supports the glass plate being made up of heat bridge fracture aluminium, its overall heat-transfer coefficient U while it is characterized in that blanketing gas at least 92%
wbe less than 1.25W/m
2.K.
41. according to the door leaf described in claim 39, and it comprises the framework that supports the glass plate being made up of PVC, while it is characterized in that blanketing gas 92%, and its overall heat-transfer coefficient U
wbe less than 1.20W/m
2.K.
42. 1 kinds of refrigeration casees, it comprises according to the door leaf described in any one claim in claim 39 to 41.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/137,373 US7976916B2 (en) | 1999-05-25 | 2005-05-26 | Refrigerated display case having a transparent insulating glazing unit |
| US11/137,373 | 2005-05-26 | ||
| PCT/FR2005/050744 WO2006125874A1 (en) | 2005-05-26 | 2005-09-15 | Insulating glazing, in particular for refrigerated chamber door |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101222866A CN101222866A (en) | 2008-07-16 |
| CN101222866B true CN101222866B (en) | 2014-07-30 |
Family
ID=35559410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200580049882.XA Active CN101222866B (en) | 2005-05-26 | 2005-09-15 | Refrigerated display case having a transparent insulating glazing unit |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US7976916B2 (en) |
| EP (1) | EP1890575B1 (en) |
| JP (1) | JP5329948B2 (en) |
| KR (1) | KR101293580B1 (en) |
| CN (1) | CN101222866B (en) |
| BR (1) | BRPI0520276B1 (en) |
| CA (1) | CA2609444C (en) |
| DE (1) | DE202005022110U1 (en) |
| DK (1) | DK1890575T3 (en) |
| ES (1) | ES2478628T3 (en) |
| MX (1) | MX2007013634A (en) |
| WO (1) | WO2006125874A1 (en) |
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- 2005-09-15 WO PCT/FR2005/050744 patent/WO2006125874A1/en not_active Application Discontinuation
- 2005-09-15 DE DE202005022110.4U patent/DE202005022110U1/en not_active Expired - Lifetime
- 2005-09-15 ES ES05800509.1T patent/ES2478628T3/en active Active
- 2005-09-15 MX MX2007013634A patent/MX2007013634A/en active IP Right Grant
- 2005-09-15 CA CA2609444A patent/CA2609444C/en active Active
- 2005-09-15 KR KR1020077026913A patent/KR101293580B1/en active IP Right Grant
- 2005-09-15 JP JP2008512859A patent/JP5329948B2/en active Active
- 2005-09-15 BR BRPI0520276-0A patent/BRPI0520276B1/en active IP Right Grant
- 2005-09-15 CN CN200580049882.XA patent/CN101222866B/en active Active
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Also Published As
| Publication number | Publication date |
|---|---|
| BRPI0520276B1 (en) | 2020-08-25 |
| US7870704B2 (en) | 2011-01-18 |
| JP5329948B2 (en) | 2013-10-30 |
| MX2007013634A (en) | 2008-04-07 |
| CN101222866A (en) | 2008-07-16 |
| EP1890575B1 (en) | 2014-04-16 |
| BRPI0520276A2 (en) | 2009-09-15 |
| CA2609444C (en) | 2012-11-13 |
| EP1890575A1 (en) | 2008-02-27 |
| US20080164788A1 (en) | 2008-07-10 |
| DE202005022110U1 (en) | 2014-03-14 |
| KR20080013916A (en) | 2008-02-13 |
| KR101293580B1 (en) | 2013-08-13 |
| US20060005484A1 (en) | 2006-01-12 |
| CA2609444A1 (en) | 2006-11-30 |
| WO2006125874A1 (en) | 2006-11-30 |
| DK1890575T3 (en) | 2014-07-21 |
| US7976916B2 (en) | 2011-07-12 |
| ES2478628T3 (en) | 2014-07-22 |
| JP2008545465A (en) | 2008-12-18 |
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